Pesticidal preparations



United States Patent 3,496,270 PESTICIDAL PREPARATIONS Clarence James Counselman, Vero Beach, Fla., assignor to Ciba Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Feb. 28, 1967, Ser. No. 619,206

Int. Cl. A01n 9/36 US. Cl. 424-211 3 Claims ABSTRACT OF THE DISCLOSURE Compositions comprising compounds of the formula wherein X is a member selected from the group consisting of chlorine, bromine, lower alkyl, lower alkoxy, CR; or N0 Y is a member selected from the group consisting of bromine, lower alkyl, lower alkoxy, CP or N0 1 and A is (1) a radical of the formula wherein R and R each are a lower alkyl radical and (2) a member selected from the group consisting of the piperidine, pyrrolidino, morpholino, cyclohexamethyleneimino and cyclopentamethyleneimino radical, and B represents a member selected from the group consisting of hydrogen or methyl, and compounds of the formula 0 /lfiZr'CH2 C\ R2Z z NHN wherein R and R each are a lower alkyl radical containing two to four carbon atoms, R and R each are a lower alkyl radical containing one to four carbon atoms, one Z represents a sulfur atom and the remaining Zs are sulfur or oxygen.

BRIEF SUMMARY The present invention relates to and has for its objects the provision of pesticidal preparations containing as active principle, a mixture of (I) A compound of the general formula wherein X represents a member selected from the group consisting of chlorine, bromine, lower alkyl, lower alkoxy, CF and N0 Y represents a member selected from the group consisting of bromine, lower alkyl, lower alkoxy, CE, and N0 1 and A represents (1) a radical of the formula wherein R and R each represents a lower alkyl radical and (2) a member selected from the group consisting of the piperidine, pyrrolidino, morpholino, cyclohexamethyleneimino and cyclopentamethyleneimino radical, and B represents a member selected from the group consisting of hydrogen and methyl, with 3,496,270 Patented Feb. 17, 1970 (II) A compound of the general formula Ri-Z 0 DETAILED DESCRIPTION The preparation of the compounds of the general formula (I) is advantageously carried out by heating the appropriate arylisocyanates with an N:N-disubstituted amide of a lower carboxylic acid, for example, dimethylformamide, N:N dimethylacetamide, N forrnyland N-acetyl pyrrolidine or piperidine. The course of the reaction can easily be followed by the CO that is developed.

Instead of the isocyanates, the corresponding carbamic acid chlorides can be used with similar success.

The preparation of the compounds of the general Formula II is advantageously carried out by the condensation of a compound of the formula wherein R R and Z have the meanings given above and K represents a cation, for example, an alkali metal ion, with a compound of the formula wherein R and R have the meanings given above and Hal represents a halogen atom, such as bromine or chlorine, with the splitting off of a substance of the formula K Hal.

Preferred preparations of the invention of the composition defined above are those which contain as component (a) the compound of the formula CH3 CH3 and as component (b) the compound of the formula CzHsO CH3 II I! CzHsO S CH3 The quantitative ratio in which the two components (a) and (b) are present can vary within comparatively wide limits. While ratios of from 10:1: 1:10 can be employed, it has been found to be especially advantageous if the ratio of (a) to (b) is within the range of 4:1 to 1:4, preferably 1:1.

The new preparations can be used for combating, for example, harmful insects, nematodes and gastropodes and can be used, for example, for protecting plants, materials and stored goods, general sanitary purposes and veterinary purposes. The new preparations are especially suitable for combating harmful acarids.

In plant protection the new preparations can be used, for example, for combating acarids and other pests that cause damage to fruits and vegetables, and they can also be used for combating cotton pests.

It is particularly surprising that the effect produced by a mixture of the components (a) and (b), for example,

effects of each agent acting al'oiie. If'is thus evident that synergism occurs when components (a) and (b) are admixed. By using the mixtures of the invention instead of the single components (a) and (b) it is possible to reduce substantially the amount of active principle required to kill the pests; furthermore, the mixtures have a surprisingly rapid action and show very good persistency. When used in combating acarids and insects, the new preparations act upon their various stages of development, such as ova, larvae and adults.

vA very wide variety of substances can be protected from pests, particularly from acarids. Examples of substances or bodies to be protected or that may serve as supports are liquids such as water in' ponds, objects in inhabited rooms, cellars, attics, stables, lofts and the like and also fur, feathers, wool and the like, as Well as living organisms of the plant and animal kingdom in their various stages of development. 1 I Combating of the a-carids and other pests is carried out by the usual methods, for example, by treating the bodies to be protected with the compounds in the form of dusting or spraying preparations, for example, in the form of solutions or suspensions prepared with water or suitable organic solvents, for example, alcohol, petroleum or tar distillates. Good results are also achieved with aerosols.

The spraying and dusting preparations can contain the usual inert fillers, for example, kaolin or bentonite or further additives, for example, sulphite waste liquor, cel lulose derivatives and the like, and they can also contain the usual wetting agents and adhesives to improve their weting power and adhesion.

The following examples illustrate the invention. Unless otherwise stated, the parts and percentages are by weight.

EXAMPLE 1 I CH3 N-phenyl-N' :N'-dimethyl-formamidine (a) Free base.100 milliliters of carefully purified dimethylformamide and 50 milliliters of phenylisocyanate were heated under reflux with the exclusion of moisture until the evolution of carbon dioxide was finished. The solution was then fractionated in vacuo. After a firstrunning of unreacted dimethylformamide, the product distilled at 140 C. under a pressure of 18 millimeters of Hg. Yield: 39.5 grams.

(b) Hydrogen sulfate.20 grams of the free base obtained as described under 1(a) were dissolved in 50 rnilliliters of absolute alcohol. To this solution were added, dropwise with cooling, 13.5 grams of concentrated sulfuric acid. The resulting crystals were filtered ofi and washed with ether. Yield: 26 grams. Melting point: 169 to 182 C. (recrystallized from absolute alcohol).

Analysise-Calculatcd for C H N S: C, 43.89%; H, 5.73%; N, 11.38%. Found: C, 43.94%; H, 5.84%; N, 11.28%

II CH3 CFa N-3-trifiuoromethyl 4 chlorophenyl N:N'-dimethylformamidine (a) Free base.This was prepared from 60 grams of 4-chloro-3-trifiuoromethylphenyl-isocyanate and 100 milliliters of dimethylformamide by the method described under 1(a). Boiling point: 164 C. at 18 millimeters of Hg.

Yield: 77 grams.

Analysis.--Calculated for ClQHlQNgClFgZ C, 47.92%; H, 4.02%; Cl, 14.15%. Found: C, 47.93%; H, 4.27%; c1,14.40%.

(b) The hydrogen sulfate was prepared from 20 grams of the free base II(a) and 7.9 grams of concentrated sulfuric acid by the method described under 1(b). Yield: 21.5 grams, melting point 203 to 205 C. (recrystallized from absolute alcohol).

Analysis.Calculated for C H O N ClSF C, 34.44%; H, 3.47%; Cl, 10.17%. Found: C, 34.69%; H, 3.66%; Cl, 9.88%.

III C11 l H C F; N-3-trifiuoromethylphenyl-N' :N-dimethyl-formamicline I CH C1 N -3-chlorophenyl-N' :N-dimethyl-formamidine (a) Free base.--This was prepared from 60 grams of meta-ch10rophenylisocyanate and 100 milliliters of dirnethylformamide by the method described under 1(a). Yield: 55 grams. Boiling point: 124C. at 0.05 millimeter of Hg.

Analysis.Calculated for CQHllNzCl: C, 59.18%; H, 6.07%. Found: C, 58.9%; H, 6.2%.

(b) Perchlorate.--'Ihis was prepared from 20 grams of the free base IV(a) and 12 milliliters of perchloric acid of 60% strength in absolute alcohol. Melting point: 183 to 185 C. (recrystallized from a mixture of alcohol and ether).

Analysis.Calculated for C H O N Cl C, 38.18%; H, 4.27%; Cl, 25.05%. Found: C, 38.17%; H, 4.25%; Cl, 25.21%.

0 H3 N -parachlorophenoxyphenyl-N' N-dimethylforrnamidine (a) Free base.This was prepared from 60 grams-of para-chlorophenoxyphenyl-isocyanate and 100 milliliters of dimethylformamide. Yield: 50 grams. Melting point: to 81.5 C. Boiling point 209 C. at 0.05 millimeter of Hg.

Analysis-Calculated for C H ON Cl: Cl, 12.91%. Found: Cl. 13.13%.

(b) Hydrogen sulfate.This was prepared from 20 grams of the free base V(a) and 7.2 grams of'concentrated sulfuric acid by the method described under 1(1)). Yield: 21 grams. Melting point: 186 to 194 C. (recrystallized from absolute alcohol).

Analysis.-Calculated for C H O N ClS: C, 48.32%; H, ;.60%; Cl, 9.51%. Found: C, 48.6%; H, 4.5%; Cl, 9.7 0.

VI. 0 H

Free base.-This was prepared by heating 50 grams of para-bromophenyl-isocyanate with milliliters of dimethylformamide. Yield: 45 grams. 173 C. at 14 millimeters of Hg.

Analysis.-Calculated for C9H11N2Br: C, 47.60%; H, 4.88%; N, 12.34%. Found: C, 47.3%; H, 4.9%; N, 12.1%.

Boiling point:

VII. C F g /C H3 =CIIN C H; C F; N-3 :5 -ditrifiuoromethylphenyl-N' :N'-dimethylformamidi Perchlorate.This was prepared by heating 50 milliliters of 3:5-ditrifluoromethylphenylisocyanate with 100 milliliters of dimethylformamide until the evolution of gas ceased. The solution was cooled and 22 milliliters of perchloric acid of 60% strength were added dropwise. The product was precipitated with ether. Yield: 70 grams. Melting point: 256 to 261 C. (after recrystallization from a mixture of alcohol and ether).

Analysis.Calcu1ated for C H O N CIF C, 34.35%; H, 2.88%; N, 7.28%. Found: C, 34.37%; H, 2.65%; N, 7.24%.

VIII

N-para-chlorophenyl-N:N'-dimethyl-acetamidine Perchl0rate.-This was prepared by heating 50 grams of para-chlorophenyl-isocyanate with 100 milliliters of NzN-dimethyl-acetamide at 130 C. until the evolution of gas ceased. The solution was cooled and the calculated amount of perchloric acid of 60% strength was added. A total of 29 grams of the desired amidine in the form of perchlorate was precipitated by the addition of ether. Melting point: 129 C. (after recrystallization from a mixture of alcohol and ether).

Analysis-Calculated for C H O N Cl N, 9.43%. Found: N, 9.61%.

N-3 5-ditrifiuoromethylphenyl-N' :N'-dimethy1- acetamidine Perchl0rate.-This was prepared from 100 milliliters of NzN-dimethyl-acetamide, 5O milliliters of 3:5-ditrifiuoromethylphenyl-isocyanate and 21.5 milliliters of perchloric acid of 60% strength by a method analogous to that described under VIII. Yield: 70.5 grams in the form of perchlorate. Melting point: 285 to 288 C. (after recrystallization from a mixture of alcohol and ether).

Analysis.Calculated for C H O N ClF C, 36.15%; H, 3.29%; N, 7.03%. Found: C, 36.25%; H, 3.17%; N, 7.09%.

CH3 CH3 N-3 :4-dichlor0phenyl-N :N-dimethyl-acetamidine Perchlorwte.This was prepared from 100 milliliters of NzN-dimethylacetamide, grams of 3:4-dichlorophenyl-isocyanate and 25 milliliters of perchloric acid of strength by a method analogous to that described under VIII. Yield: 21 grams in the form of perchlorate. Melting point: 213 to 221 C. (after recrystallization from alcohol).

Analysis.Calculated for C H N CI 'O N, 8.45%. Found: N, 8.4%.

XI C H3 CH OCH;

N-2-methoxy-S-methylphenyl-N N'-dimethylformamidine Free base.This was prepared from 50 milliliters of 2- methoxy-S-methylphenyl-isocyanate and milliliters of dimethylformamide by the method described under 1(a). Yield: 43.5 grams. Boiling point: 92 to 95 C. at 0.05 millimeter of Hg.

Analysis.--Calculated for C H O N Cl: (perchlorate prepared as described under I(b)) C, 45.13%; H, 5.85%; N, 9.57%. Found: C, 45.09%; H, 6.09%; N, 9.67%.

The melting point of the perchlorate is 234 to 236.5 C.

XII C Ha I N-para-methoxyphenyl-N':N-dimethylformamidine Boiling Analysis (theoretical values in brackets) point, Compound C./111D'1. Hg 0 H N 01 Ol- N=CHN\ l CH3 N=CHN Boiling point, Compound CJmm. Hg Molecular weight Melting point, 0.

CH3 ClQ-N CH-N 163-165/14 196. 7 35 I a CH;

EXAMPLE 2 The results are shown in the following table.

20.8 parts of the sodlum salt of drethyldithiophosphoric 10 Percent Spider mites perleaf acid are dissolved in 50 parts by volume of methyl ethyl colleena indicated intervals ketone. To this solution there is added dropwise over a after treatment of active test period of one-half hour a solution of 13.7 parts of chlo- Composition Substances coun Z-day 7-day 14-day roacetic acid-N-dimethyl hydrazide in 50 parts by vol- 1 3 0.05 24.4 6.3 11.8 22.6 ume of methyl ethyl ketone. The temperature of the mIX- 15 fiffi 0.025 43. 5 19.9 11.3 42.6 ture will rise to 30 C. The mixture is heated over a gg gg gg-g g-g g-g g'g period of six hours to 60-65 C., the sodium chloride 6,05 29:2 :0 0:0 317 which precipitates is filtered off and the filtrate evapog-gfg 9-2 rated at 60 C. The residue is taken up in 60 parts by volume of chloroform and washed twice with 20 parts of water and again with 20 parts of aqueous sodium bicarbonate. The organic layer is separated and dried over calcium chloride and evaporated in vacuo. The residue obtained is purified by trituration with 20.9 parts of water. The product obtained melts at 66 C. and has the formula C H O N PS By selection of the appropriate starting materials other compounds within general Formula (b) can also be prepared.

EXAMPLE 3 Spraying concentrates having the compositions (a), (b) and (c) are prepared.

(a) 40 parts of the active substance of the formula I CH are mixed with 15 parts of an emulsifier consisting of a mixture of 6 parts of the calcium salt of monolauryl benzenemonosulfonic acid and 14 parts of the polyglycol ether of para-isooctylphenol and diluted with 45 parts of xylene. A clear solution is thus obtained which can be used as a spraying concentrate and emulsified by pouring into water.

(b) 36 parts of the active substance of the formula C 2H O C Ha CQHISO S CH3 are mixed with 10 parts of an emulsifier consisting of 6 parts of the calcium salt of monolauryl benzenemonosulfonic acid and 14 parts polyglycol ether of sorbitanmonolaurate, 36 parts of isophorone and 18 parts of dimethylformamide to provide a spray concentrate which can be readily diluted with 'water.

(c) The compositions of parts (a) and (b) are mixed to provide a composition having a 1:1 ratio of active ingredients.

EXAMPLE 4 The spray concentrates (a), (b) and (c) of Example 3 were bulked to concentrations specified in the table below with water.

Cotton plants infested with spider mite are sprayed all over with the resulting composition. Assessments are made 2, 7 and 14 days after treatment by counting the surviving and the dead mites on each of 5 marked leaves.

What is claimed is:

1. An acaricidal composition comprising (a) not more than an effective acaricidal amount of a compound of the formula wherein X represents a member selected from the group consisting of chlorine, bromine, lower alkyl, lower alkoxy, CF and N0 Y represents a member selected from the group consisting of bromine, lower alkyl, lower alkoxy, CE; and N0 and A represents (1) a radical of the formula wherein R and R each represents a lower alkyl radical V and (2) a member selected from the group consisting of the piperidino, pyrrolidino, morpholino, cyclohexamethyleneimino and cyclopentamethyleneimino radical, and B represents a member selected from the group consisting of hydrogen and methyl, and (b) an effective acaricidal amount of i CzHsO g wherein the quantitative ratio in which the two components (a) and (b) are present is within the ratio of from 10: 1 :1 10, together with a carrier therefor.

2. An acaricidal composition according to claim 1 comprising (a) not more than an effective acaricidal amount and (c) a carrier therefor.

3. In the art of controlling acarids with not more than an effective acaricidal amount of (a) a compound of the formula *1 1 12 the improvement-which consists of the step of contacting r Referencesfiited said acarids with an effective acaricidal amount of (a) UNITED STATES PATENTS and-(b) a-compound ofwthe formnlan. v t .7 3,284,289 11/1966 Duerr et a1 424248 021160 /CH; 5 OTHER REFERENCES PS-OH2C-NH.N Chem. Abstracts 66 (25), P11538t, June 19, 1967 (of W A V. r .7 USSR 1s s,9 13..s.ep.t. 12, 196.6), W

. I S. K. ROSE, Primary Examiner m order to thereby obtam elfectlve acarlcldal control .sub- 10 v stantially greater than the sum of the effects of effective 1 I acaricidal amounts of each component (a) and (b) act- 1 ingalone, together with a carrier therefor. 424244! 2484 2 v 

